Production of valuable lubricating oils



' July 3, 1934;

M. PIER El" AL PRODUCTION OF VALUABLE LUBRICATING OILS Filed March 16', 1931 2 Sheets-Sheet l INVENT MATH ms R l ii (gas IER fmg CHRISTMR W M ATTORNEYS DRI W M. PIER ET AL PRODUCTION OF VALUABLE LUBRICATING OILS July 3, 1934.

Filed March 16, 1931 2 Sheets-Sheet 2 vx ag UNITED STATES PATENT ol-"Flcr.

PRODUCTION OF LUBRIOATING Mathias Pier, Heidelberg, and Friedrich Christmann, Ludwigshafen-on-the-Rhinc, Germany, assi ms to I. G. Farbenindustrie Aktiengesellscha t, Frankfort-on-the-Main, Germany Application March 16, 1931, Serial No. 523,178 In Germany April 5, 1930 Claims. (ol. 196-78) This invention relates to improvements in the compounds, especially oxides, either alone or'in manufacture and production of valuable lubriadmixture with each other or copper or the like cating oils. at atmospheric or increased pressure, if desired It is already known that lubricating oils may with the addition of hydrogen. In the cracking 5 be obtained by polymerizing unsaturated hydroa splitting of the carbon chains takes place 61- carbons. Frequently, however, for example when multaneously. employing initial materials comparatively poor The cracking may be carried out in coils or in hydrogen, resinous substances are formed, the tanks or both. It is particularly advantageous quality of the lubricating oils thus being considto carry out the cracking in several stages of erably impaired. difierent pressures. For example, the hydrocar- 65 We have now found that excellent lubricating bons inay first be cracked under a moderately oils are obtained by subjecting unsaturated hyelevated pressure of about 10 atmospheres, and drocarbons to condensation in stages carried outthen under a lower pressure and at a higher at successively higher temperatures, the contemperature, The cracked products obtained are 15 densed products being separated at least before mainly unsaturated hydrocarbons having a high the second stage. In this manner a condensation iodine value, preferably above 130, liquid under product, which is mainly poor in hydrogen is normal conditions of temperature and pressure, obtained in the first stage of the polymerization and boiling for the most part between 30 and carried out atlow temperatures and this is sepa- 300 C. Gaseous olefines such as ethylene, pro-.

i 20 rated, for example, by distillation in vacuo, and pylene an yl n are l b ained in rela- 5 the 6th group of the periodicsystem or their toIcarryi out. the condensation in the presence of no in the following stages carried out at successively tively small amounts. These may also be subhigher temperatures a lubricating oil rich in hyjected to the condensation. The dehydrogenation drogen and of the best quality is obtained. The of the said initial materials may also be effected process according to the present invention is by treatment under dehy n nditions particularly adapted for the production of high v with halogen or halogen-exchanging halogen quality lubricating oils, from those unsaturated mp u ds, if d d in th p s n a n hydrocarbons which by a condensation carried transferrers, such as iodine, antimony trichloride out in one operation would yield only lubricatand the like, t halogen then being Split O in ing oils of low quality. The term condensation the form of its hydrogen compounds. Instead of where employed in the present application is also halogen other substituents such as oxygen or intended to include within its scope polymerizasulphur may be employed.

tion. v The dehydrogenated products are then con- As the initial materials may be mentioned undensed in stages of successively increasing tem saturated hydrocarbons from any source, which peratures, usually of below 150 C. and preferare liquid under normal conditions of temperaably in the presenceof condensing agents, such as 90 ture and pressure. They should have a high anhydrous inorganic halides, for example aluminiodine value, often exceeding and preferably ium chloride,'zinc chloride, boron fluoride, iron exceeding 200. The said hydrocarbons may be chloride, phosphorus oxychloride, or activated obtained by the dehydrogenation for example of aluminium, sodium, zinc dust or the like. i hydrocarbons of anymolecular weight rich in The successive increase in temperature from 95 hydrogen, especially parafiinic or naphthenic stage to stage may be small, as for example 3 hydrocarbons, as for example benzines or middle or 5- 0., but often a considerably greater inoils or of petroleum residues, such as petrolatum, crease in temperature, as for example from 30 or of destructive hydrogenation products of coals, to 70 C.'is set up. The condensation carried out 45 tars, mineral oils and the like or of lubricating in stages may also be efl'ected by varying the conoils rich in hydrogen, but ofv low viscosity, or of densation agents. It may be advantageous to synthetically prepared products which havebeen operate with condensing agents of increasing prepared by the reduction of the oxides of carbon activity. As a rule the activity of the condensing with or without pressure. The dehydrogenation agent may be said to increasein the following I 50 may b ff t d f r xampl by racking hydroorder:zinc dust, sodium, activated aluminium,

carbons, in particular those rich in parafllns and iron chloride, boron fluoride, 'zinc chloride and aluof high molecular weight, as for example paraflln minium chloride.- ItEshould, however, be underwax, at temperatures below .600 (3., preferably stoodthat the said order need'not necessarily hold in the presence of catalysts such as metals .of good underall conditions. It is alsoadvantageous substances of large surface area, such as Florida earth, bleaching earth or silica gel, either alone or togetherv with the condensing agents hereinbefore mentioned or to subject the condensation products to a subsequent treatment, In some cases it is important to carry out the condensation with the addition of compounds which retard the reaction, such as zinc oxide, soda; ammonia and the like. The single stages may also be carried.

tions to produce the degree of condensation desired in the particular stage may be about 0.5 to 5 hours. On the other hand when working under otherwise the same conditions with an addition of 2 per cent by weight of anhydrous alumin-= ium chloride, the duration of the treatment must be 5 to 12 hours; It' should of course be understood that the said durations are merely stated in order to illustrate the relative rate of the reaction, and that these may be varied by one skilled in the art depending on the conditions otherwise employed. i

, In the said condensation in stagesxthe products poorer in hydrogen are usually first condensed, and each subsequent stage then furnishes a lubrieating oil richer in hydrogen.

The condensation products formed and separated in the first stage, if they do not already have lubricating properties may be converted by treatment with hydrogen under pressure into products richer in hydrogen which may serve as initial materials for the synthesis of lubricating oils.

The invention will be further explained with reference to the accompanying drawing showing in .a somewhat diagrammatic manner an elevation, partly in section, of a plant which is particularly advantageous for carrying into eflect the process according to the present invention. The invention is, however, not restricted to the particular arrangement shown in the said drawing.

Referring to this awing in detail letter a demotes a cracking shell heated'with hot gases in which a crude lubricating oil rich in hydrogencracked at a temperature between 500 and 550 C. The evaporated cracked products pass from a into cooler b and from thence into the separator c from which the gaseous constituents,

not condensed in b are drawn off through pipe d. The condensed cracked products are collected in the storing vessel 1 from which they are conveyed by means of pump g into a stirring vessel It heated with steam. In this vessel It the condensation with aluminium chloride introduced at In takes place at about 30 C. The contents of vessel h are thereupon allowed to flow into vessel e in which the condensed hydrocarbon product is separated from the waste aluminium chloride. The heavier aluminium chloride deposits on the conical bottom of vessel e from which it may be drawn oii throughpipe ez. The condensed hydrocarbon product is removed through pipe e1 mounted on vessel e ata medium height.

. The condensation product freed from the alueg minium chloride is then passed into a stirring vessel It and from thence by means of pump Z into the preheater m heated with hot gases. The preheated products are then introduced into the distillation column n. In the preheater m steam is simultaneously produced which enters the column n at q.; The condensation products freed from lower boiling constituents carried oil through pipe 0 are drawn ofi from column 12.

through pipe p and then to storage vessel 1,

while the said lower boiling constituents containing benzines and middle oil are passed through a condenser s and from thence into the separator t. From this separator the uncon-' densed gases escape through pipe t1 while the condensed products are conveyed by way of stirring vessel u and pump 21 into a second stirring vessel w in'which they are condensed for a second time with aluminium chloride at a. higher temperature, for example 100 C. The aluminium chloride is introduced at 1111. After the condensation the contents of vessel ,w are drawn oil into vessel :1: in which theseparation of the reaction product from the waste aluminium chloride takes place. The aluminium chloride is drawn off from vessel a: through pipe me while the condensation products are removed through pipe x1 mounted on vessel 0: at a medium height.

The following examples will further illustrate the nature of this invention, but the invention is not restricted to these examples. The parts are by weight.

Example 1 100 parts of an American petroleum residue (petrolatum) are cracked several times at from 500 to 540 C. In addition to 5 parts of coke and 25 parts of cracking gas, 70 parts of astrong- 1y unsaturated oil having an iodine value of 145 are obtained. This oil is polymerized at from 15 to 30? C. with an addition of 4 parts of aluminium chloride while stirring. After decomposing the aluminium chloride with water, 8 parts of resin are obtained and by distillation 55 parts of a light oil having an iodine value of 120 and a distillation residue of '7 parts of a. lubricating oil poor in hydrogen and somewhat resinous and having a steep temperature-viscosity curve are Example 2 100 kilograms of a producer tar boiling between 200 and 325 C. are stirred in a stirring vessel for 8 hours and at a temperature of C. with a mixture of 1 kilogram of boric acid and 3 kilograms of oxalic acid; After allowing the mixture to cool the liquid is separated from the precipitate and then subjected to distillation. 14.5 kilograms of a lubricating oil is obtained of which 50 per cent have a viscosity of20 Engler at 50 C. The non-condensed part is treated with 6 kilograms of aluminium chloride at 130 C. After working up 2'7 kilograms of a lubricating oil are'obtained of which 50 per cent consist of a gas machine oil having a viscosity of 12 Engler at 50 C. By the polymerization carried out in stages the'formatio'n of resinous residues is lowered to 12 per cent, whereas when carrying out the condensation in one operation more than 30 per cent of resinous residues are obtained.

Example 3 100 kilograms of producer tar boiling between 200 and 325 C. are thoroughly stirred in a stirring vessel at a temperature of about 125 C. for a period of about 8 hours with a mixture of 1 kilogram of boric acid and 3 kilograms of oxalic acid. On cooling, the sediment is separated off and on distillation of the oil, 14.5 kilograms of a lubricating oil are obtained which can be divided up into fractions of diflerent viscosities.-

That portion of the initial material which has not yet undergone condensation is treated with 6 kilograms of aluminium chloride at a temperature of about 130 C. and furnishes 27 kilograms of a lubricating oil after being worked up.

What we claim is:

1.- A process for the production of lubricating oils from a liquid hydrocarbon product essentially comprising unsaturated hydrocarbons which comprises subjecting said liquid hydrocarbon product in a first stage to partial chemical condensation to condense mainly the more unsaturated hydrocarbons in the presence of a chemical condensing agent at a temperature at which condensation without substantial cracking takes place to pro- I duce a lubricating stock comparatively poor in hydrogen, separating the condensed products from the uncondensed constituents and subjecting the latter in at least one further stage to chemical condensation to produce a lubricating stock richer in hydrogen in the presence of a chemical condensing agent at a temperature at which condensation without substantial cracking takes place, and which is at least 3 C. higher than the temperature used in said first stage, the elevation of the temperature depending on the relative activities of the condensing agents used in the separate stages.

2. The process according to the preceding claim in which the initial material is such as would yield a low quality lubricating oil when subjected to chemical condensation in one stage.

3. The process defined in claim 1 in which the I unsaturated hydrocarbons contained in the initial material boil between about 30 and about 325 C.

4. The process according to claim 1 in which the initial material boils between about 30 and about 325 C. and posseses an iodine number exceeding 100 and yields a low quality lubricating oil when subjected to chemical condensation in a single stage.

5. The process according to claim 1 in which the initial material is obtained by dehydrogenating a hydrocarbon mixture of high molecular weight and rich in hydrogen.

6. The process according to claim 1 in which the difierence between the temperature employed in the second stage and the first stage is between 3 and 70 C.

7. The process according to claim 1 in which a cyclic hydrocarbon is employed in admixture with the material.

8. The process according to claim 1 in which the chemical condensing agent employed in the densing the resulting liquid unsaturated hydrocarbons at a temperature of from 15 to 30 C. with an addition of anhydrous aluminium chloride, distilling off the light unsaturated oil thus obtaining a lubricating oil as a residue, and condensing said light unsaturated oil by treatment with aluminium chloride, at a temperature of between 30 and C.

' MATHIAS PIER.

FRIEDRICH CHRISTMANN. 

